Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107057174/sk3179sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107057174/sk3179Isup2.hkl |
CCDC reference: 672562
Single crystals were taken from an approximately 40 year-old commercial product ("Soneryl, 5-n-butyl-5-aethyl-barbituricum"; Interpharm Kom.-Ges. Vienna), which also contained the form I described by Bideau (1971).
All H atoms were identified in a difference map. CH2 hydrogen atoms were positioned geometrically with C—H = 0.99 Å (CH2). Methyl H atoms were idealized and included as rigid groups allowed to rotate but not tip with C—H = 0.98 Å (CH3). Hydrogen atoms attached to N were refined with constrained distances N—H = 0.97 (1) Å. The Uiso parameters were Uiso(H) = 1.2 Ueq(N or C) for NH, CH2 or Uiso(H) = 1.5 Ueq(C) for CH3.
Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 1998) and Mercury (Bruno et al., 2002); software used to prepare material for publication: publCIF (Westrip, 2007).
C10H16N2O3 | F(000) = 1824 |
Mr = 212.25 | Dx = 1.253 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 33142 reflections |
a = 6.8534 (1) Å | θ = 2.9–27.5° |
b = 29.6631 (7) Å | µ = 0.09 mm−1 |
c = 22.2107 (5) Å | T = 120 K |
β = 94.408 (1)° | Prism, colourless |
V = 4501.93 (16) Å3 | 0.20 × 0.07 × 0.07 mm |
Z = 16 |
Bruker–Nonius KappaCCD diffractometer | 7853 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 5428 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.1°, θmin = 3.0° |
ϕ & ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −35→35 |
Tmin = 0.896, Tmax = 0.994 | l = −26→25 |
27772 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.077 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.P)2 + 8.8472P] where P = (Fo2 + 2Fc2)/3 |
7853 reflections | (Δ/σ)max < 0.001 |
573 parameters | Δρmax = 0.26 e Å−3 |
8 restraints | Δρmin = −0.29 e Å−3 |
C10H16N2O3 | V = 4501.93 (16) Å3 |
Mr = 212.25 | Z = 16 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.8534 (1) Å | µ = 0.09 mm−1 |
b = 29.6631 (7) Å | T = 120 K |
c = 22.2107 (5) Å | 0.20 × 0.07 × 0.07 mm |
β = 94.408 (1)° |
Bruker–Nonius KappaCCD diffractometer | 7853 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 5428 reflections with I > 2σ(I) |
Tmin = 0.896, Tmax = 0.994 | Rint = 0.055 |
27772 measured reflections |
R[F2 > 2σ(F2)] = 0.077 | 8 restraints |
wR(F2) = 0.138 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.26 e Å−3 |
7853 reflections | Δρmin = −0.29 e Å−3 |
573 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O11 | 0.4089 (3) | 0.45787 (7) | 0.18105 (12) | 0.0333 (6) | |
O12 | 0.4119 (3) | 0.60900 (7) | 0.16129 (12) | 0.0328 (6) | |
O13 | 0.9996 (3) | 0.54083 (7) | 0.17596 (10) | 0.0277 (6) | |
N11 | 0.4146 (4) | 0.53348 (9) | 0.17523 (12) | 0.0199 (6) | |
H11 | 0.2745 (16) | 0.5352 (11) | 0.1755 (14) | 0.024* | |
N12 | 0.7041 (4) | 0.57359 (8) | 0.16696 (12) | 0.0216 (6) | |
H12 | 0.767 (4) | 0.6018 (6) | 0.1591 (14) | 0.026* | |
C10 | 0.7279 (4) | 0.49118 (10) | 0.18540 (14) | 0.0190 (7) | |
C11 | 0.5058 (4) | 0.49207 (11) | 0.17982 (14) | 0.0210 (7) | |
C12 | 0.5034 (5) | 0.57422 (10) | 0.16748 (14) | 0.0207 (7) | |
C13 | 0.8228 (4) | 0.53657 (10) | 0.17542 (14) | 0.0194 (7) | |
C14 | 0.7958 (5) | 0.47544 (11) | 0.25019 (14) | 0.0234 (8) | |
H14A | 0.7416 | 0.4451 | 0.2569 | 0.028* | |
H14B | 0.9402 | 0.4730 | 0.2538 | 0.028* | |
C15 | 0.7328 (5) | 0.50711 (12) | 0.29894 (15) | 0.0296 (8) | |
H15A | 0.7897 | 0.5370 | 0.2935 | 0.044* | |
H15B | 0.7783 | 0.4953 | 0.3388 | 0.044* | |
H15C | 0.5897 | 0.5094 | 0.2960 | 0.044* | |
C16 | 0.8019 (5) | 0.45765 (11) | 0.13910 (15) | 0.0252 (8) | |
H16A | 0.9461 | 0.4555 | 0.1456 | 0.030* | |
H16B | 0.7474 | 0.4275 | 0.1468 | 0.030* | |
C17 | 0.7481 (5) | 0.47025 (11) | 0.07333 (15) | 0.0288 (8) | |
H17A | 0.6040 | 0.4696 | 0.0654 | 0.035* | |
H17B | 0.7929 | 0.5014 | 0.0661 | 0.035* | |
C18 | 0.8394 (5) | 0.43838 (13) | 0.02989 (15) | 0.0339 (9) | |
H18A | 0.7924 | 0.4074 | 0.0367 | 0.041* | |
H18B | 0.9833 | 0.4385 | 0.0386 | 0.041* | |
C19 | 0.7913 (6) | 0.45093 (13) | −0.03593 (16) | 0.0411 (10) | |
H19A | 0.6491 | 0.4505 | −0.0450 | 0.062* | |
H19B | 0.8523 | 0.4292 | −0.0619 | 0.062* | |
H19C | 0.8414 | 0.4812 | −0.0434 | 0.062* | |
O21 | −0.1150 (3) | 0.80457 (8) | 0.13937 (12) | 0.0347 (6) | |
O22 | −0.1010 (3) | 0.65261 (7) | 0.13294 (11) | 0.0327 (6) | |
O23 | 0.4811 (3) | 0.72318 (8) | 0.13967 (12) | 0.0340 (6) | |
N21 | −0.1040 (4) | 0.72900 (9) | 0.13573 (12) | 0.0216 (6) | |
H21 | −0.2449 (15) | 0.7286 (11) | 0.1330 (14) | 0.026* | |
N22 | 0.1901 (4) | 0.68898 (9) | 0.13797 (13) | 0.0243 (6) | |
H22 | 0.255 (4) | 0.6600 (6) | 0.1372 (14) | 0.029* | |
C20 | 0.2063 (4) | 0.77216 (11) | 0.14474 (15) | 0.0232 (7) | |
C21 | −0.0153 (5) | 0.77063 (11) | 0.13958 (15) | 0.0243 (8) | |
C22 | −0.0117 (5) | 0.68777 (10) | 0.13557 (15) | 0.0211 (7) | |
C23 | 0.3050 (5) | 0.72668 (11) | 0.14013 (15) | 0.0242 (8) | |
C24 | 0.2738 (5) | 0.79210 (11) | 0.20747 (15) | 0.0289 (8) | |
H24A | 0.4183 | 0.7945 | 0.2108 | 0.035* | |
H24B | 0.2200 | 0.8229 | 0.2103 | 0.035* | |
C25 | 0.2114 (6) | 0.76443 (13) | 0.26039 (16) | 0.0376 (9) | |
H25A | 0.0682 | 0.7629 | 0.2586 | 0.056* | |
H25B | 0.2608 | 0.7787 | 0.2984 | 0.056* | |
H25C | 0.2649 | 0.7339 | 0.2583 | 0.056* | |
C26 | 0.2740 (5) | 0.80264 (11) | 0.09376 (15) | 0.0264 (8) | |
H26A | 0.2209 | 0.8334 | 0.0985 | 0.032* | |
H26B | 0.4186 | 0.8048 | 0.0977 | 0.032* | |
C28 | 0.2751 (5) | 0.81423 (13) | −0.01923 (17) | 0.0364 (9) | |
H28A | 0.4190 | 0.8119 | −0.0199 | 0.044* | |
H28B | 0.2423 | 0.8461 | −0.0114 | 0.044* | |
C27 | 0.2085 (5) | 0.78516 (11) | 0.03105 (15) | 0.0285 (8) | |
H27A | 0.2604 | 0.7543 | 0.0266 | 0.034* | |
H27B | 0.0639 | 0.7833 | 0.0271 | 0.034* | |
C29 | 0.1795 (6) | 0.80027 (14) | −0.08044 (17) | 0.0415 (10) | |
H29A | 0.2057 | 0.7683 | −0.0874 | 0.062* | |
H29B | 0.2334 | 0.8184 | −0.1121 | 0.062* | |
H29C | 0.0380 | 0.8052 | −0.0812 | 0.062* | |
O31 | 0.5448 (3) | 0.44572 (8) | 0.47631 (11) | 0.0318 (6) | |
O32 | 0.4867 (3) | 0.38779 (7) | 0.28810 (10) | 0.0227 (5) | |
O33 | −0.0751 (3) | 0.41582 (7) | 0.37462 (10) | 0.0238 (5) | |
N31 | 0.5111 (4) | 0.41805 (9) | 0.38188 (12) | 0.0207 (6) | |
H31 | 0.6511 (16) | 0.4178 (11) | 0.3811 (14) | 0.025* | |
N32 | 0.2053 (4) | 0.40448 (8) | 0.33111 (12) | 0.0180 (6) | |
H32 | 0.132 (4) | 0.3908 (9) | 0.2971 (9) | 0.022* | |
C30 | 0.2156 (4) | 0.44125 (11) | 0.43190 (14) | 0.0190 (7) | |
C31 | 0.4361 (5) | 0.43521 (10) | 0.43308 (15) | 0.0208 (7) | |
C32 | 0.4069 (4) | 0.40266 (10) | 0.33071 (14) | 0.0170 (7) | |
C33 | 0.1032 (4) | 0.41922 (10) | 0.37796 (14) | 0.0184 (7) | |
C34 | 0.1447 (5) | 0.42132 (11) | 0.49040 (15) | 0.0271 (8) | |
H34A | 0.2058 | 0.4383 | 0.5253 | 0.032* | |
H34B | 0.0013 | 0.4254 | 0.4900 | 0.032* | |
C35 | 0.1925 (6) | 0.37162 (12) | 0.49886 (17) | 0.0389 (9) | |
H35A | 0.1349 | 0.3546 | 0.4641 | 0.058* | |
H35B | 0.1386 | 0.3607 | 0.5358 | 0.058* | |
H35C | 0.3348 | 0.3675 | 0.5022 | 0.058* | |
C36 | 0.1690 (5) | 0.49232 (10) | 0.42909 (15) | 0.0222 (7) | |
H36A | 0.0254 | 0.4962 | 0.4286 | 0.027* | |
H36B | 0.2279 | 0.5066 | 0.4665 | 0.027* | |
C37 | 0.2403 (5) | 0.51727 (11) | 0.37543 (15) | 0.0272 (8) | |
H37A | 0.1836 | 0.5029 | 0.3378 | 0.033* | |
H37B | 0.3844 | 0.5144 | 0.3763 | 0.033* | |
C38 | 0.1867 (5) | 0.56717 (11) | 0.37406 (16) | 0.0322 (9) | |
H38A | 0.2490 | 0.5820 | 0.4106 | 0.039* | |
H38B | 0.0432 | 0.5702 | 0.3751 | 0.039* | |
C39 | 0.2513 (7) | 0.59100 (13) | 0.31810 (18) | 0.0487 (11) | |
H39A | 0.3945 | 0.5912 | 0.3193 | 0.073* | |
H39B | 0.2027 | 0.6221 | 0.3172 | 0.073* | |
H39C | 0.1981 | 0.5750 | 0.2818 | 0.073* | |
O41 | −0.0231 (3) | 0.30944 (8) | 0.03221 (10) | 0.0291 (6) | |
O42 | 0.0260 (3) | 0.37074 (7) | 0.21871 (10) | 0.0240 (5) | |
O43 | 0.5907 (3) | 0.34467 (8) | 0.13256 (10) | 0.0286 (6) | |
N41 | 0.0047 (4) | 0.33963 (9) | 0.12537 (12) | 0.0205 (6) | |
H41 | −0.1347 (16) | 0.3417 (11) | 0.1272 (14) | 0.025* | |
N42 | 0.3087 (4) | 0.35762 (9) | 0.17445 (12) | 0.0203 (6) | |
H42 | 0.374 (4) | 0.3707 (10) | 0.2100 (9) | 0.024* | |
C40 | 0.3037 (5) | 0.31454 (11) | 0.07903 (14) | 0.0219 (7) | |
C41 | 0.0821 (5) | 0.32123 (10) | 0.07547 (15) | 0.0208 (7) | |
C42 | 0.1089 (4) | 0.35673 (10) | 0.17564 (14) | 0.0195 (7) | |
C43 | 0.4127 (5) | 0.34084 (10) | 0.12938 (14) | 0.0213 (7) | |
C44 | 0.3833 (5) | 0.32688 (12) | 0.01816 (15) | 0.0298 (8) | |
H44A | 0.5259 | 0.3210 | 0.0206 | 0.036* | |
H44B | 0.3210 | 0.3071 | −0.0137 | 0.036* | |
C45 | 0.3472 (5) | 0.37585 (13) | −0.00012 (16) | 0.0359 (9) | |
H45A | 0.2062 | 0.3812 | −0.0071 | 0.054* | |
H45B | 0.4108 | 0.3822 | −0.0373 | 0.054* | |
H45C | 0.4016 | 0.3957 | 0.0322 | 0.054* | |
C46 | 0.3426 (5) | 0.26358 (11) | 0.09195 (15) | 0.0266 (8) | |
H46A | 0.2731 | 0.2460 | 0.0590 | 0.032* | |
H46B | 0.4844 | 0.2580 | 0.0900 | 0.032* | |
C47 | 0.2823 (5) | 0.24518 (11) | 0.15202 (15) | 0.0279 (8) | |
H47A | 0.3460 | 0.2633 | 0.1854 | 0.034* | |
H47B | 0.1390 | 0.2485 | 0.1533 | 0.034* | |
C48 | 0.3374 (5) | 0.19599 (11) | 0.16174 (16) | 0.0329 (9) | |
H48A | 0.4816 | 0.1932 | 0.1637 | 0.040* | |
H48B | 0.2829 | 0.1783 | 0.1266 | 0.040* | |
C49 | 0.2640 (6) | 0.17618 (13) | 0.21891 (18) | 0.0446 (10) | |
H49A | 0.3199 | 0.1931 | 0.2540 | 0.067* | |
H49B | 0.3038 | 0.1445 | 0.2226 | 0.068* | |
H49C | 0.1209 | 0.1782 | 0.2169 | 0.067* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O11 | 0.0242 (13) | 0.0180 (13) | 0.0574 (17) | −0.0054 (11) | 0.0016 (12) | 0.0067 (12) |
O12 | 0.0229 (13) | 0.0163 (12) | 0.0587 (17) | 0.0041 (11) | 0.0009 (12) | 0.0033 (12) |
O13 | 0.0121 (12) | 0.0287 (13) | 0.0428 (15) | −0.0025 (10) | 0.0051 (10) | 0.0041 (11) |
N11 | 0.0124 (13) | 0.0185 (14) | 0.0290 (16) | 0.0022 (11) | 0.0028 (12) | 0.0022 (12) |
N12 | 0.0166 (14) | 0.0142 (14) | 0.0342 (17) | −0.0028 (11) | 0.0039 (12) | 0.0014 (12) |
C10 | 0.0145 (16) | 0.0170 (16) | 0.0254 (18) | 0.0025 (13) | 0.0007 (14) | 0.0028 (14) |
C11 | 0.0186 (17) | 0.0199 (18) | 0.0246 (19) | −0.0018 (14) | 0.0013 (14) | 0.0031 (14) |
C12 | 0.0197 (17) | 0.0170 (17) | 0.0253 (19) | 0.0018 (14) | 0.0016 (14) | 0.0019 (14) |
C13 | 0.0181 (17) | 0.0204 (17) | 0.0199 (18) | 0.0001 (14) | 0.0040 (14) | 0.0014 (14) |
C14 | 0.0178 (17) | 0.0222 (18) | 0.030 (2) | 0.0031 (14) | −0.0003 (14) | 0.0076 (15) |
C15 | 0.0257 (19) | 0.033 (2) | 0.030 (2) | 0.0072 (16) | 0.0062 (16) | 0.0036 (17) |
C16 | 0.0221 (18) | 0.0196 (17) | 0.034 (2) | 0.0026 (14) | 0.0020 (15) | 0.0005 (15) |
C17 | 0.0282 (19) | 0.0239 (18) | 0.034 (2) | 0.0024 (15) | 0.0017 (16) | −0.0001 (16) |
C18 | 0.034 (2) | 0.036 (2) | 0.031 (2) | 0.0032 (17) | 0.0016 (17) | −0.0021 (17) |
C19 | 0.049 (2) | 0.044 (2) | 0.031 (2) | −0.008 (2) | 0.0085 (19) | −0.0026 (19) |
O21 | 0.0255 (13) | 0.0195 (13) | 0.0594 (18) | 0.0054 (11) | 0.0051 (12) | −0.0014 (12) |
O22 | 0.0263 (13) | 0.0174 (13) | 0.0548 (17) | −0.0093 (11) | 0.0050 (12) | 0.0016 (11) |
O23 | 0.0116 (12) | 0.0298 (14) | 0.0609 (18) | 0.0003 (10) | 0.0045 (11) | 0.0016 (12) |
N21 | 0.0112 (13) | 0.0173 (14) | 0.0363 (17) | 0.0003 (11) | 0.0014 (12) | 0.0008 (13) |
N22 | 0.0156 (14) | 0.0156 (14) | 0.0419 (18) | 0.0008 (12) | 0.0029 (13) | 0.0026 (13) |
C20 | 0.0163 (17) | 0.0172 (17) | 0.036 (2) | −0.0033 (14) | 0.0024 (15) | −0.0010 (15) |
C21 | 0.0222 (18) | 0.0184 (18) | 0.033 (2) | 0.0007 (15) | 0.0034 (15) | 0.0019 (15) |
C22 | 0.0177 (17) | 0.0180 (18) | 0.0279 (19) | −0.0008 (14) | 0.0036 (14) | 0.0011 (14) |
C23 | 0.0193 (18) | 0.0259 (19) | 0.0276 (19) | 0.0015 (15) | 0.0016 (15) | 0.0015 (15) |
C24 | 0.0228 (18) | 0.0249 (19) | 0.039 (2) | −0.0026 (15) | 0.0026 (16) | −0.0038 (16) |
C25 | 0.039 (2) | 0.040 (2) | 0.034 (2) | −0.0057 (18) | 0.0014 (18) | −0.0029 (18) |
C26 | 0.0229 (18) | 0.0148 (17) | 0.042 (2) | −0.0019 (14) | 0.0033 (16) | 0.0012 (15) |
C28 | 0.027 (2) | 0.037 (2) | 0.047 (2) | −0.0015 (17) | 0.0081 (18) | −0.0006 (19) |
C27 | 0.0225 (18) | 0.0247 (19) | 0.038 (2) | −0.0021 (15) | 0.0006 (16) | −0.0020 (16) |
C29 | 0.038 (2) | 0.047 (2) | 0.041 (2) | 0.0018 (19) | 0.0075 (19) | 0.002 (2) |
O31 | 0.0196 (12) | 0.0442 (15) | 0.0307 (14) | 0.0000 (11) | −0.0046 (11) | −0.0138 (12) |
O32 | 0.0178 (12) | 0.0264 (13) | 0.0244 (13) | 0.0012 (10) | 0.0041 (10) | −0.0054 (10) |
O33 | 0.0122 (12) | 0.0280 (13) | 0.0314 (13) | 0.0006 (10) | 0.0029 (10) | −0.0023 (11) |
N31 | 0.0132 (13) | 0.0227 (15) | 0.0261 (16) | −0.0002 (12) | 0.0013 (12) | −0.0047 (12) |
N32 | 0.0127 (13) | 0.0194 (14) | 0.0217 (15) | −0.0023 (11) | 0.0001 (11) | −0.0058 (12) |
C30 | 0.0136 (15) | 0.0208 (17) | 0.0227 (18) | 0.0018 (13) | 0.0016 (13) | −0.0041 (14) |
C31 | 0.0220 (17) | 0.0155 (16) | 0.0254 (19) | −0.0024 (14) | 0.0046 (15) | −0.0023 (14) |
C32 | 0.0182 (16) | 0.0111 (15) | 0.0220 (18) | 0.0011 (13) | 0.0021 (14) | 0.0017 (14) |
C33 | 0.0170 (17) | 0.0126 (16) | 0.0253 (18) | 0.0008 (13) | −0.0006 (14) | 0.0014 (14) |
C34 | 0.0234 (18) | 0.032 (2) | 0.0263 (19) | 0.0000 (15) | 0.0019 (15) | −0.0009 (16) |
C35 | 0.040 (2) | 0.035 (2) | 0.043 (2) | 0.0005 (18) | 0.0047 (18) | 0.0121 (19) |
C36 | 0.0183 (17) | 0.0208 (17) | 0.0277 (19) | −0.0021 (14) | 0.0022 (14) | −0.0057 (15) |
C37 | 0.0286 (19) | 0.0228 (18) | 0.031 (2) | −0.0002 (15) | 0.0069 (16) | −0.0034 (16) |
C38 | 0.039 (2) | 0.0247 (19) | 0.034 (2) | −0.0001 (17) | 0.0075 (17) | −0.0016 (16) |
C39 | 0.072 (3) | 0.024 (2) | 0.051 (3) | 0.000 (2) | 0.016 (2) | 0.0034 (19) |
O41 | 0.0246 (13) | 0.0357 (14) | 0.0265 (14) | −0.0040 (11) | −0.0025 (11) | −0.0086 (11) |
O42 | 0.0162 (11) | 0.0292 (13) | 0.0270 (13) | 0.0002 (10) | 0.0046 (10) | −0.0029 (11) |
O43 | 0.0153 (12) | 0.0368 (14) | 0.0339 (14) | 0.0001 (10) | 0.0035 (10) | −0.0008 (11) |
N41 | 0.0127 (13) | 0.0262 (15) | 0.0228 (15) | 0.0001 (12) | 0.0025 (12) | −0.0024 (12) |
N42 | 0.0129 (13) | 0.0236 (15) | 0.0243 (15) | −0.0025 (11) | 0.0004 (11) | −0.0074 (12) |
C40 | 0.0190 (17) | 0.0220 (18) | 0.0252 (19) | 0.0019 (14) | 0.0045 (14) | −0.0038 (14) |
C41 | 0.0209 (17) | 0.0187 (17) | 0.0227 (19) | 0.0000 (14) | 0.0012 (15) | −0.0018 (14) |
C42 | 0.0173 (16) | 0.0166 (16) | 0.0247 (19) | 0.0005 (14) | 0.0020 (15) | 0.0029 (14) |
C43 | 0.0191 (18) | 0.0178 (17) | 0.0276 (19) | −0.0008 (14) | 0.0053 (15) | 0.0011 (14) |
C44 | 0.0227 (18) | 0.038 (2) | 0.029 (2) | −0.0001 (16) | 0.0046 (15) | −0.0025 (17) |
C45 | 0.029 (2) | 0.045 (2) | 0.034 (2) | −0.0073 (18) | 0.0048 (17) | 0.0045 (18) |
C46 | 0.0238 (18) | 0.0244 (19) | 0.031 (2) | 0.0036 (15) | 0.0009 (15) | −0.0072 (16) |
C47 | 0.030 (2) | 0.0265 (19) | 0.0268 (19) | 0.0015 (15) | −0.0025 (16) | −0.0037 (16) |
C48 | 0.034 (2) | 0.0254 (19) | 0.039 (2) | 0.0047 (16) | −0.0001 (17) | −0.0064 (17) |
C49 | 0.055 (3) | 0.035 (2) | 0.045 (3) | 0.005 (2) | 0.005 (2) | 0.0025 (19) |
O11—C11 | 1.214 (4) | O31—C31 | 1.210 (4) |
O12—C12 | 1.210 (4) | O32—C32 | 1.212 (3) |
O13—C13 | 1.217 (4) | O33—C33 | 1.222 (3) |
N11—C12 | 1.370 (4) | N31—C32 | 1.373 (4) |
N11—C11 | 1.378 (4) | N31—C31 | 1.381 (4) |
N11—H11 | 0.962 (10) | N31—H31 | 0.961 (10) |
N12—C13 | 1.371 (4) | N32—C33 | 1.370 (4) |
N12—C12 | 1.377 (4) | N32—C32 | 1.383 (4) |
N12—H12 | 0.962 (10) | N32—H32 | 0.963 (10) |
C10—C11 | 1.518 (4) | C30—C31 | 1.520 (4) |
C10—C13 | 1.519 (4) | C30—C33 | 1.521 (4) |
C10—C16 | 1.544 (4) | C30—C34 | 1.540 (4) |
C10—C14 | 1.550 (4) | C30—C36 | 1.548 (4) |
C14—C15 | 1.521 (4) | C34—C35 | 1.519 (5) |
C14—H14A | 0.9900 | C34—H34A | 0.9900 |
C14—H14B | 0.9900 | C34—H34B | 0.9900 |
C15—H15A | 0.9800 | C35—H35A | 0.9800 |
C15—H15B | 0.9800 | C35—H35B | 0.9800 |
C15—H15C | 0.9800 | C35—H35C | 0.9800 |
C16—C17 | 1.525 (5) | C36—C37 | 1.515 (4) |
C16—H16A | 0.9900 | C36—H36A | 0.9900 |
C16—H16B | 0.9900 | C36—H36B | 0.9900 |
C17—C18 | 1.520 (5) | C37—C38 | 1.525 (5) |
C17—H17A | 0.9900 | C37—H37A | 0.9900 |
C17—H17B | 0.9900 | C37—H37B | 0.9900 |
C18—C19 | 1.520 (5) | C38—C39 | 1.525 (5) |
C18—H18A | 0.9900 | C38—H38A | 0.9900 |
C18—H18B | 0.9900 | C38—H38B | 0.9900 |
C19—H19A | 0.9800 | C39—H39A | 0.9800 |
C19—H19B | 0.9800 | C39—H39B | 0.9800 |
C19—H19C | 0.9800 | C39—H39C | 0.9800 |
O21—C21 | 1.217 (4) | O41—C41 | 1.208 (4) |
O22—C22 | 1.208 (4) | O42—C42 | 1.222 (4) |
O23—C23 | 1.212 (4) | O43—C43 | 1.222 (4) |
N21—C21 | 1.376 (4) | N41—C42 | 1.376 (4) |
N21—C22 | 1.377 (4) | N41—C41 | 1.378 (4) |
N21—H21 | 0.963 (10) | N41—H41 | 0.961 (10) |
N22—C23 | 1.367 (4) | N42—C43 | 1.367 (4) |
N22—C22 | 1.380 (4) | N42—C42 | 1.372 (4) |
N22—H22 | 0.967 (10) | N42—H42 | 0.959 (10) |
C20—C21 | 1.515 (4) | C40—C43 | 1.513 (4) |
C20—C23 | 1.516 (4) | C40—C41 | 1.528 (4) |
C20—C26 | 1.548 (4) | C40—C44 | 1.540 (4) |
C20—C24 | 1.551 (5) | C40—C46 | 1.558 (4) |
C24—C25 | 1.522 (5) | C44—C45 | 1.523 (5) |
C24—H24A | 0.9900 | C44—H44A | 0.9900 |
C24—H24B | 0.9900 | C44—H44B | 0.9900 |
C25—H25A | 0.9800 | C45—H45A | 0.9800 |
C25—H25B | 0.9800 | C45—H45B | 0.9800 |
C25—H25C | 0.9800 | C45—H45C | 0.9800 |
C26—C27 | 1.521 (5) | C46—C47 | 1.527 (5) |
C26—H26A | 0.9900 | C46—H46A | 0.9900 |
C26—H26B | 0.9900 | C46—H46B | 0.9900 |
C28—C27 | 1.509 (5) | C47—C48 | 1.518 (5) |
C28—C29 | 1.520 (5) | C47—H47A | 0.9900 |
C28—H28A | 0.9900 | C47—H47B | 0.9900 |
C28—H28B | 0.9900 | C48—C49 | 1.519 (5) |
C27—H27A | 0.9900 | C48—H48A | 0.9900 |
C27—H27B | 0.9900 | C48—H48B | 0.9900 |
C29—H29A | 0.9800 | C49—H49A | 0.9800 |
C29—H29B | 0.9800 | C49—H49B | 0.9800 |
C29—H29C | 0.9800 | C49—H49C | 0.9800 |
C12—N11—C11 | 126.3 (3) | C32—N31—C31 | 127.0 (3) |
C12—N11—H11 | 114.0 (19) | C32—N31—H31 | 116.0 (19) |
C11—N11—H11 | 119.6 (19) | C31—N31—H31 | 116.9 (19) |
C13—N12—C12 | 126.3 (3) | C33—N32—C32 | 125.9 (3) |
C13—N12—H12 | 117.0 (19) | C33—N32—H32 | 117.8 (18) |
C12—N12—H12 | 116.6 (19) | C32—N32—H32 | 115.9 (18) |
C11—C10—C13 | 114.3 (3) | C31—C30—C33 | 113.9 (3) |
C11—C10—C16 | 109.6 (3) | C31—C30—C34 | 108.5 (3) |
C13—C10—C16 | 107.9 (2) | C33—C30—C34 | 109.0 (3) |
C11—C10—C14 | 108.0 (2) | C31—C30—C36 | 108.5 (3) |
C13—C10—C14 | 107.5 (3) | C33—C30—C36 | 107.4 (3) |
C16—C10—C14 | 109.5 (2) | C34—C30—C36 | 109.4 (3) |
O11—C11—N11 | 120.1 (3) | O31—C31—N31 | 120.2 (3) |
O11—C11—C10 | 122.0 (3) | O31—C31—C30 | 122.3 (3) |
N11—C11—C10 | 117.9 (3) | N31—C31—C30 | 117.5 (3) |
O12—C12—N11 | 122.4 (3) | O32—C32—N31 | 122.0 (3) |
O12—C12—N12 | 121.4 (3) | O32—C32—N32 | 122.0 (3) |
N11—C12—N12 | 116.3 (3) | N31—C32—N32 | 116.0 (3) |
O13—C13—N12 | 119.9 (3) | O33—C33—N32 | 119.6 (3) |
O13—C13—C10 | 121.9 (3) | O33—C33—C30 | 121.8 (3) |
N12—C13—C10 | 118.3 (3) | N32—C33—C30 | 118.5 (3) |
C15—C14—C10 | 113.2 (3) | C35—C34—C30 | 113.5 (3) |
C15—C14—H14A | 108.9 | C35—C34—H34A | 108.9 |
C10—C14—H14A | 108.9 | C30—C34—H34A | 108.9 |
C15—C14—H14B | 108.9 | C35—C34—H34B | 108.9 |
C10—C14—H14B | 108.9 | C30—C34—H34B | 108.9 |
H14A—C14—H14B | 107.8 | H34A—C34—H34B | 107.7 |
C14—C15—H15A | 109.5 | C34—C35—H35A | 109.5 |
C14—C15—H15B | 109.5 | C34—C35—H35B | 109.5 |
H15A—C15—H15B | 109.5 | H35A—C35—H35B | 109.5 |
C14—C15—H15C | 109.5 | C34—C35—H35C | 109.5 |
H15A—C15—H15C | 109.5 | H35A—C35—H35C | 109.5 |
H15B—C15—H15C | 109.5 | H35B—C35—H35C | 109.5 |
C17—C16—C10 | 114.3 (3) | C37—C36—C30 | 115.6 (3) |
C17—C16—H16A | 108.7 | C37—C36—H36A | 108.4 |
C10—C16—H16A | 108.7 | C30—C36—H36A | 108.4 |
C17—C16—H16B | 108.7 | C37—C36—H36B | 108.4 |
C10—C16—H16B | 108.7 | C30—C36—H36B | 108.4 |
H16A—C16—H16B | 107.6 | H36A—C36—H36B | 107.4 |
C18—C17—C16 | 112.0 (3) | C36—C37—C38 | 113.5 (3) |
C18—C17—H17A | 109.2 | C36—C37—H37A | 108.9 |
C16—C17—H17A | 109.2 | C38—C37—H37A | 108.9 |
C18—C17—H17B | 109.2 | C36—C37—H37B | 108.9 |
C16—C17—H17B | 109.2 | C38—C37—H37B | 108.9 |
H17A—C17—H17B | 107.9 | H37A—C37—H37B | 107.7 |
C17—C18—C19 | 112.9 (3) | C37—C38—C39 | 112.4 (3) |
C17—C18—H18A | 109.0 | C37—C38—H38A | 109.1 |
C19—C18—H18A | 109.0 | C39—C38—H38A | 109.1 |
C17—C18—H18B | 109.0 | C37—C38—H38B | 109.1 |
C19—C18—H18B | 109.0 | C39—C38—H38B | 109.1 |
H18A—C18—H18B | 107.8 | H38A—C38—H38B | 107.8 |
C18—C19—H19A | 109.5 | C38—C39—H39A | 109.5 |
C18—C19—H19B | 109.5 | C38—C39—H39B | 109.5 |
H19A—C19—H19B | 109.5 | H39A—C39—H39B | 109.5 |
C18—C19—H19C | 109.5 | C38—C39—H39C | 109.5 |
H19A—C19—H19C | 109.5 | H39A—C39—H39C | 109.5 |
H19B—C19—H19C | 109.5 | H39B—C39—H39C | 109.5 |
C21—N21—C22 | 126.6 (3) | C42—N41—C41 | 126.2 (3) |
C21—N21—H21 | 117 (2) | C42—N41—H41 | 113.4 (19) |
C22—N21—H21 | 117 (2) | C41—N41—H41 | 120.3 (19) |
C23—N22—C22 | 126.5 (3) | C43—N42—C42 | 125.8 (3) |
C23—N22—H22 | 118 (2) | C43—N42—H42 | 121.0 (19) |
C22—N22—H22 | 116 (2) | C42—N42—H42 | 113.2 (19) |
C21—C20—C23 | 114.7 (3) | C43—C40—C41 | 113.8 (3) |
C21—C20—C26 | 108.5 (3) | C43—C40—C44 | 109.8 (3) |
C23—C20—C26 | 108.1 (3) | C41—C40—C44 | 110.0 (3) |
C21—C20—C24 | 107.9 (3) | C43—C40—C46 | 107.2 (3) |
C23—C20—C24 | 107.2 (3) | C41—C40—C46 | 106.9 (3) |
C26—C20—C24 | 110.4 (3) | C44—C40—C46 | 109.0 (3) |
O21—C21—N21 | 119.8 (3) | O41—C41—N41 | 120.7 (3) |
O21—C21—C20 | 122.4 (3) | O41—C41—C40 | 122.3 (3) |
N21—C21—C20 | 117.9 (3) | N41—C41—C40 | 116.9 (3) |
O22—C22—N21 | 122.4 (3) | O42—C42—N42 | 122.3 (3) |
O22—C22—N22 | 121.8 (3) | O42—C42—N41 | 121.1 (3) |
N21—C22—N22 | 115.9 (3) | N42—C42—N41 | 116.6 (3) |
O23—C23—N22 | 120.1 (3) | O43—C43—N42 | 119.9 (3) |
O23—C23—C20 | 121.8 (3) | O43—C43—C40 | 121.7 (3) |
N22—C23—C20 | 118.2 (3) | N42—C43—C40 | 118.3 (3) |
C25—C24—C20 | 113.9 (3) | C45—C44—C40 | 113.5 (3) |
C25—C24—H24A | 108.8 | C45—C44—H44A | 108.9 |
C20—C24—H24A | 108.8 | C40—C44—H44A | 108.9 |
C25—C24—H24B | 108.8 | C45—C44—H44B | 108.9 |
C20—C24—H24B | 108.8 | C40—C44—H44B | 108.9 |
H24A—C24—H24B | 107.7 | H44A—C44—H44B | 107.7 |
C24—C25—H25A | 109.5 | C44—C45—H45A | 109.5 |
C24—C25—H25B | 109.5 | C44—C45—H45B | 109.5 |
H25A—C25—H25B | 109.5 | H45A—C45—H45B | 109.5 |
C24—C25—H25C | 109.5 | C44—C45—H45C | 109.5 |
H25A—C25—H25C | 109.5 | H45A—C45—H45C | 109.5 |
H25B—C25—H25C | 109.5 | H45B—C45—H45C | 109.5 |
C27—C26—C20 | 112.7 (3) | C47—C46—C40 | 117.0 (3) |
C27—C26—H26A | 109.0 | C47—C46—H46A | 108.1 |
C20—C26—H26A | 109.0 | C40—C46—H46A | 108.1 |
C27—C26—H26B | 109.0 | C47—C46—H46B | 108.1 |
C20—C26—H26B | 109.0 | C40—C46—H46B | 108.1 |
H26A—C26—H26B | 107.8 | H46A—C46—H46B | 107.3 |
C27—C28—C29 | 111.9 (3) | C48—C47—C46 | 112.7 (3) |
C27—C28—H28A | 109.2 | C48—C47—H47A | 109.0 |
C29—C28—H28A | 109.2 | C46—C47—H47A | 109.0 |
C27—C28—H28B | 109.2 | C48—C47—H47B | 109.0 |
C29—C28—H28B | 109.2 | C46—C47—H47B | 109.0 |
H28A—C28—H28B | 107.9 | H47A—C47—H47B | 107.8 |
C28—C27—C26 | 113.5 (3) | C47—C48—C49 | 113.3 (3) |
C28—C27—H27A | 108.9 | C47—C48—H48A | 108.9 |
C26—C27—H27A | 108.9 | C49—C48—H48A | 108.9 |
C28—C27—H27B | 108.9 | C47—C48—H48B | 108.9 |
C26—C27—H27B | 108.9 | C49—C48—H48B | 108.9 |
H27A—C27—H27B | 107.7 | H48A—C48—H48B | 107.7 |
C28—C29—H29A | 109.5 | C48—C49—H49A | 109.5 |
C28—C29—H29B | 109.5 | C48—C49—H49B | 109.5 |
H29A—C29—H29B | 109.5 | H49A—C49—H49B | 109.5 |
C28—C29—H29C | 109.5 | C48—C49—H49C | 109.5 |
H29A—C29—H29C | 109.5 | H49A—C49—H49C | 109.5 |
H29B—C29—H29C | 109.5 | H49B—C49—H49C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O13i | 0.96 (1) | 1.89 (1) | 2.854 (3) | 178 (3) |
N12—H12···O22ii | 0.96 (1) | 1.88 (1) | 2.829 (3) | 171 (3) |
N21—H21···O23i | 0.96 (1) | 1.90 (1) | 2.857 (3) | 171 (3) |
N22—H22···O12 | 0.97 (1) | 1.91 (1) | 2.843 (3) | 161 (3) |
N31—H31···O33ii | 0.96 (1) | 1.89 (1) | 2.854 (3) | 176 (3) |
N32—H32···O42 | 0.96 (1) | 1.93 (1) | 2.877 (3) | 167 (3) |
N41—H41···O43i | 0.96 (1) | 1.90 (1) | 2.858 (3) | 178 (3) |
N42—H42···O32 | 0.96 (1) | 1.91 (1) | 2.861 (3) | 170 (3) |
C36—H36B···O31iii | 0.99 | 2.40 | 3.318 (4) | 155 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C10H16N2O3 |
Mr | 212.25 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 6.8534 (1), 29.6631 (7), 22.2107 (5) |
β (°) | 94.408 (1) |
V (Å3) | 4501.93 (16) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.20 × 0.07 × 0.07 |
Data collection | |
Diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.896, 0.994 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27772, 7853, 5428 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.077, 0.138, 1.07 |
No. of reflections | 7853 |
No. of parameters | 573 |
No. of restraints | 8 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.29 |
Computer programs: , DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Bruker, 1998) and Mercury (Bruno et al., 2002), publCIF (Westrip, 2007).
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O13i | 0.962 (10) | 1.892 (11) | 2.854 (3) | 178 (3) |
N12—H12···O22ii | 0.962 (10) | 1.875 (12) | 2.829 (3) | 171 (3) |
N21—H21···O23i | 0.963 (10) | 1.902 (12) | 2.857 (3) | 171 (3) |
N22—H22···O12 | 0.967 (10) | 1.910 (14) | 2.843 (3) | 161 (3) |
N31—H31···O33ii | 0.961 (10) | 1.894 (11) | 2.854 (3) | 176 (3) |
N32—H32···O42 | 0.963 (10) | 1.929 (12) | 2.877 (3) | 167 (3) |
N41—H41···O43i | 0.961 (10) | 1.897 (11) | 2.858 (3) | 178 (3) |
N42—H42···O32 | 0.959 (10) | 1.912 (12) | 2.861 (3) | 170 (3) |
C36—H36B···O31iii | 0.99 | 2.40 | 3.318 (4) | 154.7 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+1. |
Butobarbital, (I), is a 5,5-disubstituted barbituric acid derivative used as a sedative hypnotic drug for severe insomnia (Soneryl; Joint Formulary Committee, 2007). Cleverley & Williams (1959) reported the existence of four polymorphic forms, and Draguet-Brughmans et al. (1981) investigated the physical properties of three modifications of (I). Their form I (m.p. 397 K) is consistent with a crystal structure reported earlier by Bideau (1971). Recently, Nichol & Clegg (2005) determined the structure of a low-temperature (LT) phase, which was obtained by cooling a crystal of form I (crystallized from water) to 120 K. A subsequent data collection at room temperature showed that this phase transition is reversible. The arrangement of butobarbital molecules in these two structures is practically the same, and a conformational change of the n-butyl groups was identified as being their main difference.
The structure of a third polymorph of (I) with prismatic habit is reported here. Comparison with previous studies on the polymorphism of (I) (Bideau, 1971; Draguet-Brughmans et al., 1981; Cleverley & Williams, 1959; Williams, 1959; Mesley & Clements, 1968; Mesley, 1969; Huang & Jerslev, 1951) shows that the data (IR-spectrum and X-ray powder pattern) for this modification match closely with those given by Draguet-Brughmans et al. (1981) for their polymorph II.
The title structure has the space group P21/c and four independent molecules, one of which is shown in Fig. 1. A l l molecules adopt the same principal geometry, and their alkyl chains exhibit the expected staggered antiperiplanar conformation. The bond lengths and angles are consistent with the corresponding parameters in the previously reported modifications of (I). The six-membered rings are not perfectly planar.
Two of the molecules of (I) are joined into N—H···O-bonded tapes (Fig. 2a and Table 1) by employing two hydrogen-bond donor and two acceptor functions per molecule. These tapes consist of two independent R33(12) rings (Bernstein et al., 1995), which connect three molecules. The rings are edge-fused to larger R44(18) units. The mean plane through the alkyl fragment of (I) is approximately perpendicular with respect to the central plane of the tape defined by the C4N2 rings, so that angles of 87.08 (9) and 82.65 (8)° are formed. All ethyl moieties point in one direction and all butyl groups in the opposite direction.
N—H···O interactions between the other two independent molecules result in the ladder motif shown in Fig. 2(b). Pseudo-centrosymmetric dimers with R22(8) rings are edge-fused with pseudo-centrosymmetric R44(18) rings connecting four molecules. Both tapes and ladders propagate parallel to the a axis, which implies a perfect match of their translation periods. Furthermore, the four independent molecules are arranged in separate one-dimensional stacks parallel to the a axis.
A closer inspection reveals a set of short dimeric C—H···O contacts (Table 1), which connect adjacent ladders related by inversion symmetry. These contacts involve a butyl CH2 group and an O atom not engaged in classical hydrogen bonding. The packing of tapes and ladders is depicted in Fig. 3.
Ribbon chains are the most common hydrogen-bonding motifs in 5,5-substituted derivatives. The chains found in form I of butobarbitul and its LT-form (Bideau, 1971; Nichol & Clegg, 2005) belong to this particular class. By contrast, there are only two previous examples of the tape motif shown in Fig. 2(a), the structures of γ -methylamobarbital (Gartland & Craven, 1971) and quinal barbitone (Nichol & Clegg, 2007). The ladder motif of Fig. 2(b) has been observed in methylphenylbarbital (Bravic et al., 1968) and barbital (Craven et al., 1969). Thus, the polymorph of (I) reported here is the first example where these two rather unusual one-dimensional motifs appear simultaneously in one structure.